Method for fabricating copper-containing ternary and quaternary chalcogenide thin films

ABSTRACT

An apparatus for depositing a solid film onto a substrate from a reagent solution includes reservoirs of reagent solutions maintained at a sufficiently low temperature to inhibit homogeneous reactions within the reagent solutions. The chilled solutions are dispensed through showerheads, one at a time, onto a substrate. One of the showerheads includes a nebulizer so that the reagent solution is delivered as a fine mist, whereas the other showerhead delivers reagent as a flowing stream. A heater disposed beneath the substrate maintains the substrate at an elevated temperature at which the deposition of a desired solid phase from the reagent solutions may be initiated. Each reagent solution contains at least one metal and either S or Se, or both. At least one of the reagent solutions contains Cu. The apparatus and its associated method of use are particularly suited to forming films of Cu-containing compound semiconductors.

CROSS REFERENCE TO RELATED APPLICATION

This application is a Divisional of U.S. patent application Ser. No.12/462,146 filed by the present inventor on Jul. 30, 2009 now U.S. Pat.No. 7,972,899, the entire disclosure of which is incorporated herein byreference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention pertains to a system and method for chemically coating avariety of surfaces with semiconductor materials, metals, or insulatorsfor various applications Including electronics. More particularly, theinvention pertains to methods for making chalcogenide compound filmscontaining copper, for photovoltaic devices and other applications.

2. Description of Related Art

Numerous coating processes like electroless chemical, chemical vapor,and physical vapor depositions are commonly employed in industrialapplications. Physical vapor deposition is commonly used insemiconductor manufacturing applications, often employing expensivevacuum techniques in order to sustain a relatively high film growthrate. Many such processes, while performed at high temperatures (e.g.,greater than 300° C.), are non-equilibrium, often resulting innon-stoichiometric proportions. Also, due to the nature of thedeposition processes, the deposited films often include relatively highdefect densities. In the case of semiconducting devices, such highdefect levels can limit electrical performance characteristics. Insemiconductor device fabrication wherein p-n junctions are formed in apartial vacuum by depositing one film over a second film or a substrateof different conductivity type, the conventional evaporative andsputtering techniques may provide unsatisfactory film qualities. As analternative, relatively more expensive techniques such as Chemical VaporDeposition (CVD), Molecular Beam Epitaxy (MBE), pulsed laser deposition,and atomic layer epitaxy, are useful, especially with formation of III-Vcompound semiconductor materials, but satisfactory deposition processeshave not been available for fabrication of thin film II-VI compoundsemiconductor materials.

Chacogenide compound films of CuAC or Cu(AB)C [where A is In, Al, Ga,Sn, Fe, Sb or any other transition metal; (AB) is (InGa), (InAl), (ZnSn)or (CdSn), or any combination of transition metals; and C is S or Se orthe combination of SSe] are p-type semiconductor materials with greatimportance in solar cells and other optoelectronic applications.Bringing devices based on these materials to the market has been greatlyimpacted by the cumbersome and poor yield of their traditional growthtechniques.

The traditional techniques of growing some of these materials includethe following:

Three-stage batch co-evaporation of CuInGaSe on Mo-coated substrate aspracticed by the National Renewable Energy Laboratory (NREL). The firststage is the deposition of (InGa)₂Se₃ layer at 400° C., and reacting itwith Cu and Se at 550° C. during the second stage. The third stage,similar to the first stage, consists of the evaporation of In and Ga inthe presence of Se at 400° C. [1,2].

CuInGaSe fabricated on Mo-coated glass by a hybridco-evaporation/sputtering process as taught by Energy Photovoltaics,Inc. (EPV). In this process, In and Ga are first evaporated in thepresence of Se vapor. The first layer is followed by sputtered Cu, andthe film is selenized in Se vapor. In the final stage, In and Ga areonce again evaporated in the presence of Se [1].

Co-evaporated CuInGaSe on Mo-coated stainless steel by Global SolarEnergy, Inc. The Global Solar process is essentially three-stage, inthat group III atoms (In and Ga) are deposited first, then Cu, followedby enough group III atoms to bring the film to its desiredstoichiometry; each of these steps is done in the presence of seleniumat high temperature. Deposition is performed onto continuously advancing36 cm 300 m rolls of stainless steel foil at high deposition rates [1].

Shell Solar Industries (SSI) approach in the fabrication of CuInGaSSeinvolves sputtering a stacked precursor from alloyed Cu—Ga and Intargets, then selenization in H₂Se at elevated temperature, followed bysulfurization in H₂S at elevated temperature. The depositions andreactions are performed on 3900 cm² panes of soda-lime glass coated witha SiO₂ diffusion barrier and Mo back contact [1].

Two-stage batch co-evaporated CuInGaSe on Mo-coated glass by theInstitute for Energy Conversion (IEC). In this process, elemental Cu,In, Ga, and Se fluxes are independently controlled to provide a Cu-richtotal flux, Cu/(In+Ga)>1, at the start of the run. Then, In, Ga, and Sefluxes only are applied until the desired final composition, Cu/(In+Ga)=0.8-0.9, is attained. The films are deposited at a 550° C.substrate temperature [1].

CuZnSnS deposited by inline-type vacuum apparatus. Here, ZnS, SnS and Cuare co-sputtered on a heated and rotated substrate in the vacuum chamberand then moved to reaction gas chamber for sulfurization using N₂+H₂S(20%) and annealing around 580° C. [3].

All the above are expensive vacuum techniques; and the process involvedis based mostly on the intermixing of elements constituting the materialand subjecting the mixture to high temperature to form the compound.Unfortunately each of the various elemental particles does not have thesame surrounding. Hence, small isolated areas will have the rightmaterial composition after anneal leading to film with non-uniformstoichiometry. Thus, the process may be good for small area depositionbut poor for large area deposition needed for high yield manufacturing.

Another method of growth adopted by Nanosolar is coating a homogeneouslymixed ink of nanoparticles, in this case Cu, In, Ga, and Se, withindustrial wet coating techniques followed by baking and sintering toform the CuInGaSe compound [4].

International Solar Electric Technologies (ISET)'s CuInGaSSe absorber isprepared by applying a mixed oxide precursor coating on a metallizedglass substrate via a non-vacuum knife coating technique. The precursorcoating is deposited using a water-based ink which containsnanoparticles of mixed oxides. After drying, the precursor ink isreduced under an atmosphere of H₂ and N₂ gas mixture to obtain a uniformand a smooth coating of Cu—In—Ga alloys. The resulting alloy coating isfurther selenized under an atmosphere of H₂Se and H₂S gases [1].

Both of the foregoing methods are non-trivial, as they involvenanoparticle growth, a process which is not as cheap as one expects,because the nanoparticle growth requires expensive chemicals and takesplace at extremely slow rate. This is then followed by the expensive inkformulation process. Materials grown by this method will also sufferfrom non uniformity due to high probability of particles not having thecorrect surrounding particles throughout the growth area.

Copper indium disulfide (CuInS) thin films deposited viaaerosol-assisted chemical vapor deposition using single sourceprecursors. Growth at atmospheric pressure in a horizontal hot-wallreactor at 395° C. yielded best device films as claimed by the author.Post-deposition sulfur-vapor annealing enhanced stoichiometry andcrystallinity of the films. However, the single precursor is a veryexpensive organometallic (PPh₃)₂Cu(SEt)₂In(SEt)₂. The high precursorcost may not be compatible with the low cost devices like solar cells[5].

CuSbS was also deposited by traditional chemical bath deposition (CBD).This involves growing SbS first followed by CuS. A 6700 Å film tookabout 7 hours to grow. This slow growth rate and the accompanying wastemake this process unacceptable [6].

CuInS₂ was equally deposited by spray pyrolysis [7]. Here they sprayedaqueous solution of 0.01M of CuCl₂.2H₂O, InCl₃, and CS(NH₂)₂ in a 1:1:2(by volume) onto substrates at various temperatures of 225, 250 and 275°C. CuSbS₂ films were also obtained by Spray Pyrolysis Deposition [8].Here the precursor weight ratio (CuCl₂.2H₂O:H₂NCSNH₂:(CH₃COO)₃Sb) wasvaried between 2.57:1:5.71 and 6.86:1:5.71, at 240° C. Most of the timethe film morphology is less than desirable and the electrical propertiesof these films are impaired by non-volatile unwanted elements leftbehind in the films; the films are therefore of less practicalimportance.

Additional background information may be found in the followingreferences, whose numbers correspond to the respective citations in theforegoing discussion:

-   1. I. L. Repins et al. Comparison of device performance and measured    transport parameters in widely-varying Cu(In,Ga)(Se,S) solar cells.    Prog. Photovolt: Res. Appl. 14:25-43, 2006.-   2. J. Ward et al. Cu(In,Ga)Se2 Thin-film concentrator solar cells.    NCPV Prog. Rev. Meeting Lakewood, Colo., Oct. 14-17, 2001.    NREL/CP-520-31144.-   3. K. Jimbo et al. Cu₂ZnSnS₄-type thin film solar cells using    abundant materials. Thin Solid Films 515: 5997-9, 2007.-   4. Nanosolar Inc.; High-performance thin-film photovoltaics using    low-cost process technology. 17^(th) Int'l Photovoltaic Sci. Eng.    Conf., Tokyo, Japan, Dec. 3-7, 2007.-   5. A. F. Hepp et al. Aerosol-assisted chemical vapor deposited thin    films for space photovoltaics; NASA/TM-2006-214445.-   6. S. Messina et al. Antimony sulfide thin films in chemically    deposited thin film photovoltaic cells. Thin Solid Films    515:5777-82, 2007.-   7. S. Aksay, “Structural and morphological properties of CuInS₂    polycrystalline films obtained by spray pyrolysis method. J. Arts    and Sci. 4:1-9, 2005.-   8. S. Manolache et al. The influence of the precursor concentration    on CuSbS₂ thin films deposited from aqueous solutions. Thin Solid    Films 515:5957-60, 2007.

OBJECTS AND ADVANTAGES

Objects of the invention include the following: providing a bathdeposition apparatus capable of depositing a selected phase on asubstrate while minimizing homogeneous nucleation of the same or similarphase within the bulk of the fluid bath; providing a bath depositionapparatus capable of depositing films having improved physical,chemical, optical, or electrical properties; providing a bath depositionapparatus that is more easily controlled; providing a bath depositionapparatus that uses reagents more efficiently; providing a bathdeposition apparatus that allows localized heating of a relatively smallvolume of the bath while maintaining the remainder of the bath at arelatively lower temperature; providing a bath deposition apparatus forgrowing high quality mixed chalcogenide thin films; providing a bathdeposition apparatus for growing mixed Cu-containing chalcogenide filmssuitable for photovoltaic cells; providing a method for bath depositionthat is more easily controlled; providing a method for bath depositionthat minimizes homogeneous nucleation within the bath; providing amethod for bath deposition capable of depositing films of selected II-VIcompounds, other compounds, or metals having improved properties;providing a method for bath deposition of high quality mixedCu-containing chalcogenide films; and, providing a method for bathdeposition of chalcogenide films having a graded composition. These andother objects will become apparent on reading the specification inconjunction with the accompanying drawings.

SUMMARY OF THE INVENTION

In accordance with one aspect of the invention, an apparatus fordepositing a solid film onto a substrate from reagent solutionscomprises:

a reservoir of a first reagent solution maintained at a firsttemperature at which homogeneous reactions are substantially inhibitedwithin the first reagent solution;

a first showerhead assembly including a nebulizer configured to dispensethe first reagent solution as a fine mist at the first temperature;

a reservoir of a second reagent solution maintained at a secondtemperature at which homogeneous reactions are substantially inhibitedwithin the second reagent solution;

a second showerhead assembly configured to dispense the second reagentsolution as a flowing stream at the second temperature;

a substrate holder configured to hold the substrate in a position toreceive, in sequence, at least a portion of the fine mist of the firstreagent solution and at least a portion of the flowing stream of thesecond reagent over a selected area of the substrate, the substrateholder further including a raised structure peripheral to the selectedarea whereby a controlled volume of the second reagent solution may bemaintained upon the substrate and replenished at a selected rate; and,

a heater disposed beneath the substrate, the heater configured tomaintain the substrate at a selected temperature, higher than at leastone of the first and second temperatures, at which the deposition of adesired solid phase from the first and second reagent solutionsrespectively may be initiated.

In accordance with another aspect of the invention, a method fordepositing a solid film onto a substrate from a reagent solutioncomprises the steps of:

providing a supply of a first reagent solution maintained at a firsttemperature at which homogeneous reactions are substantially inhibitedwithin the first reagent solution;

dispensing a fine mist of the first reagent solution from a firstshowerhead assembly;

positioning the substrate to receive at least a portion of the fine mistof the first reagent over a selected area of the substrate;

providing a supply of a second reagent solution maintained at a secondtemperature at which homogeneous reactions are substantially inhibitedwithin the second reagent solution;

dispensing a flowing stream of the second reagent solution from a secondshowerhead assembly;

positioning the substrate to receive at least a portion of the flowingstream of the second reagent over a selected area of the substrate;

providing a raised structure peripheral to the selected area whereby acontrolled volume of the second reagent solution may be maintained uponthe substrate; and,

heating the substrate and the controlled volume of the second reagentsolution upon the substrate to a selected temperature, higher than atleast one of the first and second temperatures, whereby deposition of adesired solid phase from the reagent solutions may be initiated.

BRIEF DESCRIPTION OF THE DRAWINGS

A clear conception of the advantages and features of the invention, andof the components and operation of exemplary systems provided with theinvention, will become more readily apparent by referring to thedrawings accompanying and forming part of this specification, in whichlike numerals designate like elements in several views. The features arenot necessarily drawn to scale.

FIG. 1 illustrates schematically the general flow of reagents inaccordance with one aspect of the invention.

FIG. 2 illustrates schematically a vertical section of a chemical bathdeposition chamber in accordance with one aspect of the presentinvention.

FIG. 3 illustrates schematically a vertical section of a chemical bathdeposition chamber in accordance with another aspect of the presentinvention.

FIG. 4 presents a process flow diagram for a two-layer film stackprepared according to one aspect of the invention.

FIG. 5 illustrates schematically the formation of a single-phaseCu-containing semiconductor film via the deposition of two separatefilms according to one aspect of the invention.

FIG. 6 illustrates schematically the formation of a film with a gradedbandgap according to one aspect of the invention.

FIG. 7 presents a SIMS depth profile of a CuZnSnS film prepared by theinventive method.

DETAILED DESCRIPTION OF THE INVENTION

There has been a need for a chemical system that can create high qualityfilms, e.g., semiconductor films, at high formation rates, whileproviding a relatively uniform film thickness across the entiresubstrate surface over which the film is formed. In accordance withseveral embodiments of the invention, such a high quality semiconductorfilm is formed by a replacement reaction wherein the system provides acontinuous or replenishable supply of chemical processing solution. Inseveral examples, the solution reacts about the surface of a heatedsubstrate. The substrate temperature may be controlled to exhibit asubstantially uniform temperature across the surface. That is,temperature differentials along the surface over which the film isformed are limited in order to effect a substantially constant reactionrate along the surface, thereby assuring a relatively uniform filmgrowth rate. Further, the pH and composition of the solution may becontinuously monitored and maintained to improve the stability of theprocess and, hence, the quality of the deposited film, e.g.,stoichiometry, defect density, uniformity and consistency of dopantdistribution. The system may be operated above atmospheric pressure toincrease the rate of film growth.

FIGS. 1-2 illustrate schematically some aspects of a Film Growth System(FGS) for conducting chemical bath deposition as taught generally inApplicant's co-pending U.S. patent application Ser. No. 12/151,562,filed on May 7, 2008, the entire disclosure of which is incorporatedherein by reference. This process will be referred to herein as LiquidPhase Streaming Electroless Electrochemical Deposition (LPSPEED).Briefly, some characteristics of LPSPEED include the following: Areagent solution containing various metals and nonmetals, and variousligands to improve its stability, is held at a fairly low temperature(preferably chilled) to suppress homogeneous nucleation. This solutionis dispensed through a shower head, substantially as a flowing liquid,and flows onto a substrate. The substrate is heated to a temperaturesufficient to cause heterogeneous nucleation of a desired solid phaseonto the surface of the substrate. In some preferred examples,additional flow of the chilled reagent solution may be used to coolother parts of the deposition apparatus to suppress homogeneousnucleation in the solution as well as heterogeneous nucleation onsurfaces other than the substrate. In another examples the regionoutside the heater in the deposition chamber is actively cooled by anembedded cooling jacket where chilled coolant flows in and out of thejacket; this arrangement further suppresses homogeneous nucleation inthe solution as well as heterogeneous nucleation on surfaces other thanthe substrate in the deposition chamber.

The aforementioned U.S. patent application Ser. No. 12/151,562 teachesmany suitable compositions of the reagent solution adapted to depositmany different solid films.

Based on further experimentation and testing, Applicant has discoveredthat the earlier process may be further modified to expand its utility,to make compositionally graded films, and to generally solve many of thepreviously-described shortcomings in prior methods. As will be describedin more detail in several Examples that follow, one aspect of thepresent invention includes the addition of a second showerheadcomprising one or more nebulizers configured to dispense a reagentsolution as a fine mist with droplets preferably less than about 50 μmand, more preferably, less than about 20 μm. A process using thenebulizer will be referred to herein as Vapor Phase Streaming Processfor Electroless Electrochemical Deposition (VPSPEED)

The FGS of FIG. 1 includes a reaction chamber 10 and a chilled solutionreservoir 11 for retaining and chilling chemical processing solutionwhich may be held at a stable, low temperature preferably less thanabout 25° C. and more preferably in the range of 10 to 25° C. or lower.At the preferred temperatures, homogeneous reactions are substantiallyinhibited and the solution has adequate shelf life and minimalhomogeneous precipitation of particulates. The FGS further includes asolution supply subsystem for moving the chemical processing solution(while maintained at a low temperature) from the reservoir to thechamber, and a solution return subsystem for cycling partially spentsolution from the chamber back to the solution reservoir. The solutionsupply subsystem includes a supply line filter F2 for removingparticulates from the solution, a supply line pump P2 for supplying thesolution to the reaction chamber, and a liquid control panel 12 underthe direction of a system controller. The liquid control panel 12includes a series of conventional valves and flow controllers forselectably injecting and varying flows of liquids into the processingchamber 10. For example, the liquid control panel 12 may deliver thechemical processing solution and one or more chemicals for chambercleaning or for cleaning of the surface of the substrate over which adesired film is grown.

Chemical processing solution from the reservoir is supplied to theliquid control panel by the supply line pump after passing through thesupply line filter F2. The solution return subsystem includes aplurality of valves for controlling flows of various liquids from theprocessing chamber, a return line reservoir 13, a return line filter F1for removing particulates from the returning solution, and a return linepump P1 for sending the filtered solution to the process solutionreservoir 11. Proper control and regulation of the liquid flowingthrough the liquid control panel is effected by the flow controllersunder the direction of the system controller. Solution reservoir 11 mayoptionally include such familiar components as high and low levelswitches 14, 15, temperature sensor 16, pH meter 17, and chemicalanalyzer 18.

The reaction chamber 10 illustrated schematically in FIG. 2 includes asubstrate holder assembly 31′, which may include mechanical clamps (notshown) or a vacuum chuck (as shown) arranged to secure substrate 33, adelivery system that includes a showerhead 41′ for supplying anddistributing processing solution within the chamber and over substrate(workpiece) 33. The substrate holder assembly 31′ comprises aninsulative housing, which may include an embedded cooling jacket, with aheater block 45′ formed therein. A lip or ring structure 51 surroundssubstrate 33 in order to impound a selected volume of the film-formingreagent solution. The combination of the heater block and an upperinsulative surface (over which a substrate is placed) is referred toherein as a platen. Various of these components may have circular orrectangular shapes, but the functionality of the reaction chamber is notlimited to these example geometries. In other examples the ringstructure 51 may be replaced by a spacer including apertures or slots ormay be replaced by several individual spaced-apart spacers wherein theseparation facilitates exit flow of processing solution from thereaction region adjacent to the exposed upper substrate surface throughthe solution return subsystem to the chilled reservoir 11. The chambermay further include a pressure gauge, a gas inlet, a gas outlet, asshown schematically in FIG. 1, and a drain line 34 which is part of thereturn subsystem that directs partially spent processing solution fromthe chamber 10 to the reservoir 11. In this example, to minimizemaintenance and extend useful life of the chamber, all chamber partsthat are exposed to the chemical solution are preferably made ofchemically inert material, such as polytetrafluoroethylene (PTFE) orperfluoroalkoxy (PFA), or the surfaces of such parts may be coated witha PTFE or PFA film. For example, the ring 51 (positioned about thesubstrate to create a shallow catch region or substrate opening forretaining flowing portions of the processing solution over the substratesurface) may be formed of a relatively rigid or a relatively softmaterial such as PTFE, PFA, or PFA-coated or PTFE-coated structuralmaterial. The illustrated continuous ring 51 encloses an area of thesubstrate surface that may be continuously, continually or periodicallyreplenished with processing solution, as solution previously suppliedfrom an overlying showerhead overflows or pours outward from the volumeenclosed by the ring 51 and passes into the drain line 34.

It will be appreciated that the operation of ring 51 differsfundamentally from the “containment frame” of McCandless et al. in U.S.Pat. No. 6,537,845 in that McCandless contemplates a substantiallystatic containment of a fixed volume of solution, whereas the presentinvention relies on continuous or periodic replenishment using chilledsolution from the showerhead. Applicant uses this novel feature tofurther cool adjacent hardware components as well as cool the solutionin areas other than the immediate deposition layer in order to moreeffectively suppress homogeneous nucleation.

A feature of the FIG. 1 example is that the rate of film formation,e.g., the rate of growing II-VI semiconductor materials, in the FGS isrelatively high while the ratio of the volume of processing solutionabout the film formation surface on the substrate to the area of thefilm formation surface over which the film is formed is small, i.e.,small relative to the corresponding ratio present in a conventional,traditional chemical bath. The foregoing statement is made with theunderstanding that the geometry and orientation of the substrate withina traditional chemical bath is typically different than that of the FGSsince the traditional bath typically immerses the substrate in a heatedvessel containing processing solution while the FGS positions and heatsthe substrate to receive a supply of processing solution, e.g., via acontinuous or continual or periodic flow such as from above. Thus adirect comparison of such ratios is not easily ascertained. Nonetheless,according to the invention, the applicable volume-to-surface area ratiois effectively substantially smaller than that which would be present ina traditional bath, e.g., when the substrate is positioned in ahorizontal or vertical orientation inside a vessel filled withprocessing solution or otherwise oriented with respect to a levelsolution surface. For operation in the FGS, the ratio of the volume ofprocessing solution about the film formation surface of the substrate tothe area of the substrate surface over which the film is formed isreferred to herein as the Volume-to-Surface Area Ratio (VSAR). When theVSAR is high, a relatively small fraction of the processing solution iseffectively contributing to the film formation while the remainingportion may result in formation of colloids in the bulk of the solution.In the FGS the spacer allows a limited volume of processing solution tobe positioned above the substrate surface. The spacer may appear like ashallow tank, but actually serves as a temporary, periodicallyreplenished collection region, as portions of the processing solutionremain over the substrate surface for brief periods in order to effectchemical reactions along the exposed surface. The exemplary continuousspacer may be secured along the periphery of the substrate with amulti-clamp design, which allows the solution to flow over the spacer.Thus, the volume of chemical processing solution retained within thespacer confines is generally determined by the height of the spacerabove the substrate, ranging, for example, between 0.1 and 10 mm.Depending on the specific process, setting of process parameters (e.g.,substrate temperature, flow rate of processing solution, concentrationof reactants in the solution) a spacer with a suitable or optimum heightmay be chosen. Due to the complexity of multiple variables, and thedesire to maximize the rate of film formation, it may be necessary toexperimentally determine process geometries and settings. The FGS may beprogrammed to deliver a continuous or periodic flow of processingsolution through the shower head, or may be programmed to delivermetered volumes, to provide a uniform delivery of the solution over thefilm formation surface. With a continuous spacer formed over a uniformlyheated substrate and a continual or periodic replenishment of processingsolution over the reaction region of the substrate, a low VSAR effects arelatively uniform film growth over the entire region of film growth ata relatively high growth rate suitable for volume manufacture. Among theseveral examples disclosed herein, exemplary VSARs range from 0.1 to 10mm, with exemplary corresponding film growth rates ranging from 100 to1000 Å/minute and film thicknesses of satisfactory uniformities (e.g.,less than 10 percent) may exceed several microns.

Another feature of the invention is that during the film formationprocess the film growth surface may be kept at a relatively hightemperature while other surfaces within the reaction chamber arerelatively cool. This feature can minimize or prevent formation of filmon surfaces other than that of the substrate. By way of example, thetemperature differential between the growth surface and other surfacesin the reaction chamber can range from 60° C. or 70° C. to 200° C. andmay, for example be 140° C. The chamber pressure, the solution flowrate, and the substrate temperature may be adjusted to achievedeposition rates on the order of 500 Å/min to produce a relativelyuniform film having a thickness on the order of one to five microns. Theachievable uniformity (i.e., measurable based on variation in filmthickness) over a film growth area of 21 cm² is generally better than10% and in some instances better than 5%. As shown generally in FIG. 1,during operation of the FGS the processing solution passes from withinthe volume defined by the ring 51 to the solution return line and theassociated reservoir 13 in order to be pumped back into the solutionreservoir 11 for chilling and recirculation until such time that therequisite chemicals are so spent that the solution should be replaced.In the process of passing into the return line, the processing solutionleaving the volume defined by the ring or spacer may join other portionsof processing solution which are relatively cool. That is, such otherportions of processing solution are injected through the showerhead andinto regions of the chamber outside the region of the heated film growthsurface such that these portions are relatively cool. The latter,relatively cool solution may mix with portions of the solution flowingfrom the spacer volume to facilitate temperature reduction of the heatedsolution, thereby limiting formation of undesirable products in thereaction chamber. The solution reservoir may include a temperaturesensor 16, a chemical analyzer 18, a pH meter 17, and a pair of liquidlevel switches 14, 15. The temperature of the solution reservoir iscontrolled by the chiller and the reservoir is typically maintained at atemperature in the range of 10-25° C. A chemical analyzer 18 isconnected to the solution reservoir to monitor the chemical compositionof the reservoir constantly or periodically. When needed, the pre-mixedprocessing solution is added to the solution reservoir from a tankcontaining pre-mixed solution of desired concentration, although thesolution may be stored in a more concentrated form and diluted upon orprior to entry into the reservoir. For example, the system controllermay operate valves associated with the liquid control panel to dispensedistilled (DI) water and precursor solutions directly into the reservoirfor mixing in the solution reservoir. In some chemical processes,deposition rates are significantly influenced by the pH of the solution.The pH meter 17 monitors the pH of the solution bath and the pH may beadjusted under direction of the controller. Liquid level in thereservoir is controllable with first and second liquid level sensorswitches. The first liquid level sensor switch 15 provides a signal tothe controller when a minimum desired level of solution resides in thereservoir. The second liquid level sensor switch 14 provides a signal tothe system controller when a maximum level of liquid resides in thereservoir.

The entire system may operate under direction of a system controller,which actuates numerous valves and switches in response to sensorinformation, e.g., signals provided by level switches. The systemcontroller controls delivery of processing solution to the reactionchamber via the solution flowmeter and may also selectively rotate theshowerhead during the chemical process. A thermocouple is provided tocontrol the platen temperature during operation. The controller alsocontrols delivery of pre-mixed processing solution to the solutionreservoir to maintain suitable level of processing solution in thereservoir.

For periodic maintenance of the processing chamber, a chemical solutionfor chamber cleaning may be supplied from a cleaning chemical tank via acleaning chemical supply line. DI water for rinsing the chamber afterchamber cleaning may be supplied from a DI water tank via a DI watersupply line. Delivery of cleaning chemical is controlled by a cleaningchemical supply line valve. Delivery of DI water is controlled by a DIwater supply line valve. A separate drain under control of a dedicatedvalve may be provided to collect the chamber cleaning chemical and rinsewater. Generally, the flow of drain liquid from the chamber iscontrolled by a combination of the solution return line valve and acleaning chemical return line valve under direction of the controller.The collected cleaning chemical may be sent to a chemical recoveryprocessing unit for recovery of chemical ingredients.

FIG. 3 depicts a cross-sectional view of another embodiment of the FGSreaction chamber taken along its vertical centerline. This chamber,modified to carry out the VPSPEED method, differs from that shown inFIG. 2 in several respects. First, showerhead assembly 41″ includes anebulizer 60, which is preferably movable to some degree, configured todeliver a fine mist of reagent solution to substrate 33. Nebulizers maybe of various designs. One suitable type is the air-assisted nebulizersuch as the Mira Mist nebulizer [Burgener Research, Inc., 944 MeadowWood Rd., Mississauga, Ontario, Canada, L5J 2S6]. Another suitable typeis the ultrasonic-assisted nebulizer such as the Impact precisionsprayer [Sono-Tek Corp., 2012 Route 9W, Milton, N.Y. 12547]. The ringstructure 51 shown previously in FIG. 2 may be eliminated becauseApplicant contemplates that the nebulizer will deliver a substantiallylower quantity of reagent solution and there is consequently no need toprovide a structure to retain or impound a significant quantity ofreagent solution on the substrate surface during the VPSPEED depositionstep.

Depending on the specific process, the substrate can be heated to somedesired temperature during the deposition process. A feature of theinvention is that the film growth rate in the FGS is exponentiallydependent upon temperature, and it is therefore beneficial to keep onlythe substrate at a high temperature while chamber surfaces are kept at alow temperature for efficient, selective deposition. It will beunderstood by those skilled in the art, in view of several Examples thatfollow, that the reagent solution delivered during the LPSPEED phase ofthe process will generally be of a different composition than thereagent solution delivered during the VPSPEED phase of the process.Consequently, it is preferable in many cases for the heated platen tohold the substrate at one temperature for the VPSPEED operation and asecond temperature for the LPSPEED operation. In both cases, thesubstrate is held at a higher temperature than that of the respectivereagent solution being dispensed through the showerhead or atomizer.

Applicant contemplates that in many applications, the VPSPEED phase willbe carried out first, followed by the LPSPEED phase. However, Applicantdoes not intend to limit the invention to any particular order of theprocess steps, and the skilled artisan may determine through routineexperimentation that for some particular application the LPSPEED stagemay be performed first, followed by the VPSPEED stage, or indeed thatthe two stages may be carried out iteratively in order to create morecomplicated compositionally modulated structures.

FIG. 2 shows an example in which the showerhead 41′ is substantiallyfixed in position relative to the substrate holder assembly 31. It willbe appreciated that in other contemplated embodiments, it might bedesirable to use a moving, rotating, or oscillating showerhead asanother means of ensuring uniform flow of process liquid over the entiresubstrate surface. Skilled artisans can easily add such modificationswithout undue experimentation using electric motors, mechanical linkagesand the like as are well known in the art.

In the Examples that follow, more than one layer of semiconductormaterial may be formed on a substrate by a sequence of chemicalprocesses. Referring to FIG. 4, there is shown a flow chart of exemplarysteps that sequentially place multiple layers of material on thesubstrate. Formation of two layers in a sequence may include a cleanstep for removing contaminants from the substrate surface, followed byformation of a first layer. Next, a first post-film formation clean stepmay be performed for removing residual chemicals from the substratesurface, followed by a step for forming a second film layer differentfrom the first layer. This may be followed by a second post-filmformation clean step for removing residual chemicals from the substratesurface. In the pre-film formation clean step, a substrate placed on thesubstrate holder assembly inside the chamber may be cleaned with a firstcleaning solution, rinsed with de-ionized (DI) water, and dried, forexample, by a spin drying method as is common in semiconductor devicemanufacturing. Next, a first semiconductor layer is formed along thesurface of the substrate, followed by a postfilm formation clean whereinthe substrate may be cleaned with a second cleaning solution, rinsedwith DI water for a suitable duration and dried. For multi-layer filmformations, a system comprising a plurality of process chambers and asubstrate handling robot can offer high operation efficiency andthroughput resulting in a relatively low equipment cost per film layer.A single robot may provide substrate handling for multiple processingchambers.

The exemplary film growth systems described in FIGS. 1-4 may be used toform films comprising any of a wide range of materials, includingmetals, semiconductors, and insulators on a temperature-controlledsubstrate from constituents in a solution by series of reactions whichare performed while controlling one or more of: the substratetemperature, the chamber pressure, the flow rate of the processingsolution, the pH and the composition of the solution. For materials ofparticular interest for photovoltaic applications, a general processsequence may be described as follows.

The VPSPEED system is used to deposit a first layer consisting of AC or(AB)C where A is In, Ga, Sn, Sb, Fe, Al, etc.; (AB) is (InGa), (InAl),(ZnSn), (CdSn), etc.; and C is S or Se or the combination of these twoelements.

Then the LPSPEED system is used to deposit a CuS layer on top of thefirst layer. During the liquid phase deposition of CuS, thermal andchemically induced diffusion and ion exchange can take place between theCuS and the first layer. This phenomenon leads to in situ formation ofCuAC or Cu(AB)C as the case may be. The excess of flowing reagent duringthe LPSPEED step provides a further benefit by allowing the washing awayof unwanted elemental residues in the VPSPEED deposited layer that oftenimpair the electrical properties of pure spray deposited films.

To complete the homogenization of the deposited CuAC or Cu(AB)C film,the film may be subjected to rapid thermal anneal (RTA) at a temperatureof 200-250° C. in N₂/Ar atmosphere for about 5 to 10 minutes.

The film may be further subjected to flash anneal or RTA anneal at atemperature ranging between 300 to 500° C. for about 1 to 10 minutes inAr/N₂ atmosphere to increase the grain sizes and improve the film'selectrical transport properties.

The bandgap of these materials could also be graded; this generallycorrelates with Cu-rich (for low bandgap) or Cu-poor (high bandgap) partof the film. To make the part of the film adjacent to the substrateCu-rich, a thin CuS layer may deposited before the depositing the AC or(AB)C first layer; and to have a Cu-poor region at the surface of thefilm an additional layer of AC or (AB)C is deposited after the CuSdeposition.

The precursors for VPSPEED deposition are preferably the nitrate,acetate, sulphate, or chloride salt of the metal or metals of interest,and thiourea or selenourea or the combination of the two for S or Sesource respectively. The solvent is preferably deionized water with 10to 90% ethanol, acetone, or other suitable organic solvent. The presenceof organic solvent serves to further ensure that the reagent mistdroplet sizes are preferably less than 50 μm and more preferably lessthan about 20 μm for the most uniform film deposition. During thisdeposition the substrate is preferably held at a temperature rangingbetween room temperature and about 200° C.

The precursors for LPSPEED deposition are preferably as described inApplicant's co-pending U.S. patent application Ser. No. 12/151,562. Thereagent solution comprises the salt of the metal or metals of interest,at least two ligands, and thiourea or selenourea as the S or Se sourcein the deionized water medium at the appropriate pH. Growth takes placeon the substrate held at temperature that is preferably more than about100° C.

Some specific examples that follow will provide a fuller understandingof the invention with particular emphasis on its application tophotovoltaic materials.

Example

FIG. 5 shows schematically the formation of CuAC or Cu(AB)C film havingthe chalcopyrite structure. In the first step, a desired thickness of ACor ABC compound 2 is formed on substrate 1, preferably by VPSPEED orother spray-based technique. In the next step, a corresponding thicknessof CuC layer 3 is deposited by LPSPEED to achieve the desiredstoichiometry. The target compound CuAC or Cu(AB)C, layer 4, is formedduring the deposition of layer 3.

Example

FIG. 6 illustrates schematically the formation of a CuAC or Cu(AB)C filmwith a graded bandgap. In the first step, a thin layer 3 of CuC isdeposited on substrate 1. A layer 2 of AC or (AB)C is then deposited,followed by another layer 3 of CuC. Lastly, a thin layer 2 of AC or(AB)C is deposited. Homogenization, either during film growth or duringa post-deposition anneal, creates a graded layer 5 comprising twosub-layers, 5 a and 5 b. Sublayer 5 a is Cu-rich with a relatively lowerbandgap and sublayer 5 b is Cu-poor with a relatively higher bandgap.

Example

A CuInS film was grown on a Mo-coated stainless steel substrate in twosteps. First, InS was deposited by VPSPEED using a reagent solutionconsisting of: InCl₃ 0.005M, thiourea 0.0075M in 1:1 ethanol-de-ionizedwater solution. The reagent solution was maintained at 15° C. andsprayed onto the substrate in an atomized mist (average droplets wereabout 20 μm) while the substrate was held at about 150° C. Then, a layerof CuS was deposited on top of the InS film by LPSPEED using an aqueousreagent solution consisting of: copper sulfate 0.005M, triethanolamine0.09M, citric acid 0.125M, nitriotriacetic acid 0.03M and thioacetamide0.008M. This reagent solution was maintained at 15° C. and dispensedonto the InS-coated substrate, which was held at about 120° C. Thecomplete grown film was then annealed in Ar/N₂ ambient at about 210° C.for about 10 minutes.

SIMS analysis of the resulting 0.5 μm thick film showed goodhomogeneity, and XRD analysis indicated that the predominant crystallinephase was CuIn₅S₈, which is one of the phases of interest forphotovoltaic applications.

Example

A graded film consisting predominantly of the phase Cu₂ZnSnS₄ wasdeposited on Mo-coated stainless steel in the sequenceCuS—SnZnS—CuS—SnZnS. For VPSPEED SnZnS deposition, the reagent solutionconsists of SnCl₃ 0.0025M, zinc nitrate 0.0025M, and thiourea 0.0075M in1:1 ethanol-de-ionized water solution maintained at 15° C.; tions, andthe substrate kept at 160° C. For LPSPEED CuS deposition, the aqueousreagent solution consisting of copper sulfate 0.005M, triethanolamine0.09M, citric acid 0.125M, nitriotriacetic acid 0.03M and thioacetamide0.008M was used. This reagent solution was maintained at 15° C. anddispensed onto the heated substrate, which was held at about 120° C. Thecomplete grown film was then annealed in Ar/N₂ ambient at about 210° C.for about 10 minutes.

The resulting film, about 0.8 μm thick, was analyzed by SIMS and thedepth profile is shown in FIG. 7. It can be seen that Cu and S arefairly uniformly distributed throughout the film, whereas Sn and Znconcentrations vary significantly. The ratios of these concentrationscan therefore be manipulated to grade the bandgap of the film.

SEM analysis indicated that the film had a nanocrystalline structure,consistent with the diffuse XRD pattern of the sample. It is expectedthat an appropriate thermal anneal could be used to recrystallize thefilm and induce further grain growth to improve the overall electronicproperties of the film.

Those skilled in the art of semiconductors will appreciate that gradingthe composition of a film in the direction normal to the substrate caninfluence a number of electronic properties besides the bandgap. Some ofthese properties include the concentrations of carriers such aselectrons and holes, and their respective mobilities, as well as theelectrical conductivity or resistivity of the film.

Some compound semiconductors for which the inventive technique may beused include the following in any stoichiometry: CuSbS, CuSbSSe,CuInSSe, CuSnZnSe, CuInGaSSe, CuInGaS, CuAlS, CuAlSSe, CuFeS, CuFeSSe,CuLiS, CuLiSSe, CuGaS, CuGaSSe, CuSnS, CuSnSSe, CuZnS, CuZnSSe, CuAlMgS,CuAlMgSSe, CuCdS, CuCdSSe, CuCdSnS, CuCdSnSSe, etc. Through routineexperimentation the skilled artisan can modify the various recipes andprocedures taught herein to accommodate other metals, adding them forexample as nitrates, chlorides, acetates, sulfates or other solublespecies.

Although numerous examples of the invention have been illustrated anddescribed, the invention is not so limited. Numerous modifications,variations, substitutions and equivalents will occur to those skilled inthe art without departing from the spirit and scope of the presentinvention.

1. An apparatus for depositing a solid film onto a substrate fromreagent solutions comprising: a reservoir of a first reagent solutionmaintained at a first temperature at which homogeneous reactions aresubstantially inhibited within said first reagent solution; a firstshowerhead assembly including a nebulizer configured to dispense saidfirst reagent solution as a fine mist at said first temperature; areservoir of a second reagent solution maintained at a secondtemperature at which homogeneous reactions are substantially inhibitedwithin said second reagent solution; a second showerhead assemblyconfigured to dispense said second reagent solution as a flowing streamat said second temperature; a substrate holder configured to hold saidsubstrate in a position to receive, in sequence, at least a portion ofsaid fine mist of said first reagent solution and at least a portion ofsaid flowing stream of said second reagent over a selected area of saidsubstrate, said substrate holder further including a raised structureperipheral to said selected area whereby a controlled volume of saidsecond reagent solution may be maintained upon said substrate andreplenished at a selected rate; and, a heater disposed beneath saidsubstrate, said heater configured to maintain said substrate at aselected temperature, higher than at least one of said first and secondtemperatures, at which the deposition of a desired solid phase from saidfirst and said second reagent solutions respectively may be initiated.2. The apparatus of claim 1 wherein said selected temperature is atleast 60° C. higher than at least one of said first and said secondtemperatures.
 3. The apparatus of claim 1 wherein said first showerheadassembly is configured to dispense said first reagent solution as a misthaving an average droplet size less than about 50 μm.
 4. The apparatusof claim 1 wherein said second showerhead assembly is configured todispense a first portion of said second reagent solution into saidcontrolled volume defined by said raised peripheral structure and todispense a second portion of said reagent solution outside of saidcontrolled volume.
 5. The apparatus of claim 1 further comprising aprocess chamber containing said showerhead assemblies, said substrateholder, and said heater.
 6. The apparatus of claim 5 wherein at least aportion of said second reagent solution follows a recirculating pathbetween said process chamber and said second reagent solution reservoir.7. The apparatus of claim 6 wherein at least one of said first andsecond reagent solution reservoirs includes a device selected from thegroup consisting of: temperature sensors, pH meters, chemical sensors,liquid level control switches, and chillers.
 8. The apparatus of claim 6wherein said recirculating path includes a device selected from thegroup consisting of: pumps; valves; filters; pressure gauges; and returnline reservoirs.
 9. The apparatus of claim 5 wherein said processchamber may be maintained at a selected pressure.